Recovery of organic compounds



wit Mar; 28,1939 I i PATENT orrica ascovsni or onasmc com'omvns' JanD.Ruys,Plttabnrg,Oalif.,asalgnorito8hell Development company,

San Francisco, Calif apcorporation of Delaware Application February 19, 1esa,- Serial No. 191,411

7 Claims; .(01. 202-14) This invention relates to a process 101' the recovery 01' volatile organic compounds andlor normally solid and invola'tile materials from mix-. tures comprising both such con'ip'onents.

5 while it isbroadl'y applicable to the recovery of a volatilev organic compound and/or a sub stantiaily non-volatile solid from a liquid system comprising these different components, the invention is of particular value in that it provides 10 a practical and economical process, which may be operated in a batch, intermittent or continuous manner, 'foreiiecting the recovery of a vaporizabie organic compound from a solution of said organic compound and a dissolved sub- -l stantiaiiy non-volatilesolid organic or inorganic material, orfor eiiecting the removal 0 a vapcrizahle organic compound from a solutio comprising the-organic compound, a dissolved. substantially non-volatile so'lid inorganic material 20 and once: more other volatile organic or inorganic liquids.

The process of the inventioncomprises contact ing the solid-containing mixture with :a liquid which is heated to a temperature sufllciently high 25 to flash oil the volatile organic compound, alone .or together with any other volatile liquidwhich may be present in the treated solution, and leave the, solid material dissolved or suspended-in the,

heated liquid. In a generally preferred mode of a0 operation, the heated liquid with which the solid-" containing solution is contacted is substantially immiscible with the organicliquid to' be flashed oil and is a liquid in which the solid material of the treated solution -is substantially insoluble. 5 Thus, on contact 0! the solid-containing solution .with the heated liquid. which liquid is heated to a temperaturegreater than the boiling temperature of the organic liquid to berecovered' under the pressure existing in the system, the organic liquid "is flashed ofi. while the solid material stays be hind, for example, as a suspension, in the'heated liquid from-which it may be easily and ob free oi; the solid material.

The flashed-oi! organic cpound is '45 The of the invention is particularly adapted the recovery oiorganic ,oxy-com pounds such as monohydric iaicohols,'polyhygiric' alcohols, :ethers. esters, aldehydes," ketones, oleline oiddea hah ydrins. slycldols and 50 fromtheir aqueous'solutions containing one 'or a plurality oi dissolved'salts. -Many oi such organic city-compounds, the polyhydric 1 I alcohols, the oleline .ox l des'and the halohydrlns, may be-prmared in commercialquantities in ac the corresponding hydrolyzable halogenated organic' compounds such as the oleilne dihalides, oleflne halohydrins, glycerine halohydrins and the like to a hydrolysis treatment with water in the presence 01 a basic neutralinng agent. The basic 5 'agentwhich ls-usualiy a basic metal hydroxide or a basic metal salt reacts-with the hydrogenhalide liberated during the course of the hydrolysis reaction to neutralize .all or a part .of the same and form a metal salt which dissolves in .the aqueous reaction mixture along with at least apart of organiereaotionproduct. Thus,.the reaction results in anaqueous solution-oi the organic reaction product and a salt. Recovery 0! the organic reaction product in a substanl5 tiaily pure and anhydrous form'necessitates, as the first step, the separation 01 the organic prodnet or the organic product and water. as well as any. of the unreacted halogenated organic compound which may be present, from the salt.

" There are several known methods for eiiecting "the separation of polyhydric'alcohols from their aqueous salt solutions, none or which are, from a technical standpoint, entirely satisiactory. The

known methods in their simplest. form comprise evaporating or distilling the water-polyhydric alcohol-salt mixtures. Since the polyhydric alcohols are relatively high boiling and boil at temperatures greater than 100 6., and since they do not in the great majority of cases form constant boiling mixtures with water, the eiiect oi the distillation and evaporation methods oi. the

art isto concentrate the water polyhydric alco hol-sait solutions by removing water therefrom,

leaving the polyhydrlc alcohol and the salt behind. .As the water is removed, the ratio of salt to water increases until eventually the salt begins to crystallize out. The presence oi the solid salt in the mixture being distilled causes bumping and makes it extremely diflicult to operate without carrying over polyhydric alcohol and increasing the losses. This makes it necessary 'to provide .the still with so-called salt into which --the salt settles during the operation, or to-periodically discontinue the operation and sep-' state the salt from the mixture in the still-kettle by' filtration or centritugation. In any case, the

removedsalt, retains a. considerable amount of the polyhydric alcohol which must be recoveredthereirom to avoid excessive losses. The polygon hydric alcoholic customarily recovered irom salt by washing" it with water and returning washwatertotherecoverysystem. Thiswashin: requiresthe reintroductionintothesystem oi acons'iderableantcuntoiwaterwhichmustaminlso system a considerable amount of salt which was redissolved during the washing operation. It is seen that in such a recovery system the equipment must of necessity be of considerably greater capacity than would be required if the salt could be removed directly and substantially free of the polyhydric alcohol in a single stage distillation operation.

My invention provides a practical and economical process which can be operated continuously on a technical scale for the direct recovery of polyhydric alcohols and like compounds such as the glycidols, halohydrins, oleflne oxides, etc., from aqueous salt solutions containing one or more of them. The polyhydric alcohol or like compound is substantially completely separated from the salt in a single operation, rendering subsequent treatment of the salt to recover any polyhydric alcohol or like compound retained therewith unnecessary.

In accordance with this embodiment of the in- V vention, which will for purposes of illustration be described with particular reference to the recovery of a polyhydric alcohol from an aqueous salt solution containing the same, the polyhydric alcohol-water-salt solution is brought into contact with a stream or body of a heated liquid. This may be accomplished in a variety of suitable manners, for example, by continuously spraying the polyhydric alcohol-water-salt solution into a stream or body of the heated liquid contained in a suitable apparatus for the purpose.

The heated liquid with which the polyhyd c alcohol-water-salt solution is contacted is, ior this particular embodiment of the invention, one of relatively high boiling temperature which is preferably substantially immiscible with the polyhydric alcohol and water and in which the salt or salts to be separated from the treated solution are substantially insoluble. The liquid used should also be relatively stable and substantially incapable of reacting with the polyhydric alcohol and/or water under the conditionsof operation.

Suitable liquids for the purpose are the sufllciently high boiling hydrocarbons, hydrocarbon mixtures. halogenated hydrocarbons and the like. A suitable liquid will in most cases have an atmospheric boiling temperature greater than about 150? C. The high boiling oils such as refined Diesel oil,spray oil, light spindle oil and the like are particularly suitable; they are substantially im miscible with the polyhydric alcohols and water.

and the salts encounteredin the polyhydric a1- cohol-water-salt solutions are practically insoluble in them.

The heated liquid with which the aqueous polyhydrlc alcohol-salt solution is contacted is maintained at such a temperature that when the solution is contacted therewith at an appropriate rate, depending upon the capacity oi. the equipment and the conditions under which it is desired to operate, the polyhydric alcohol'and water are rapidly and substantially completely flashed 01!. Thus, it is seen'that the heated liquid should be at a temperature greater than the boiling temperature of the polyhydric alcohol and water under the pressure existing in the system. For example, when the process is executed to recover ethylene glycol from an aqueous solution containing ethylene glycol and a salt, and such sol .tion is contacted with a heated oil whereby the ethylene glycol and water are flashed oil leaving the salt in 'the oil, the oil is maintained at a temperature of from about 150 C. to 350 C. It

be evaporated, besides reintroducing into the is seen that since neither the polyhydric alcohol nor the water are miscible to any appreciable extent with the mineral oil, these two compounds will be completely vaporized and flashed oil provided sufllcient heat is available in the oil.

. The salt present in the aqueous polytwdric alcohol-salt solution will, on contact of the solution with the heated liquid whereby the polyhydri alcohol and water are flashed 01!, remain in suspension in the heated liquid which under proper operating conditions will be substantially free of both polyhydric alcohol and water. The salt is very easily removed from the heated liquid in a variety of suitable manners such as by decantation, filtration, centrifugation, washing out, etc. For e rample, the salt can be filtered from the liquid and any liquid retained on it can be recovered by dissolving-the salt and separating the immiscible liquid. If the salt is a waste product as may be the case when the salt is sodium chloride, operation in this manner provides a convenient mode of disposing of the salt. If desired, for example, when the salt is more valuable than sodium chloride, it may, of course, be recoyered from the aqueous solution in any desired manner.

The vapors of the flashed oil water and polyhydric alcohol may be condensed and the condensate further treated for the separation of the water and the polyhydric alcohol. Since the condensate is free of salt and consists of substantially only the polyhydric alcohol and water, the removal of water to obtain the poiyhydrlc alcohol in an anhydrous or substantially water-free eondition is easily accomplished by a variety of,

known methods. The usual distillation methods under atmospheric or subatmospheric pressure may be employed. In some cases, during the flashing oi! operation, a small amount 01 the flash evaporation medium may be carried over as vapors along with the vapors of the polyhydric alcohol and water, but after condensation it can be easily separated from the condensate and reutilized.

The process may be executed under any desired pressure. In many cases, excellent results may be obtained by operation with the flash evapora-' tion system under about atmospheric pressure. In other cases, particularly when the organic compound is relatively high boiling, it may be desirable to effect theflashing operation under a reduced pressure, in which case the liquid flash evaporation medium need not be heated to such a high temperature to elect the flashing oil.

The process is conveniently elected in a continuous manner by continuously feeding the polyhydric alcohol-water-salt solution at the desired rate into a flash evaporation apparams .ot any convenient capacity, material and design wherein it is brought into contact with the liquid flash evaporation medium which has been heated to the desired temperature prior to its introduction into the evaporator. The liquid flash evaporation the evaporator. The liquid flash evaporation medium may be continuously circulated through a closed circuit comprising a heater wherein the circulating liquid is heated to the desired temperature, an evaporator wherein the circulating liquid leaving the heater is contacted with the poly!!!- drlc' alcohol-water-s'alt soluflon. and a suitable circulatingpump. The evaporator may be so designed that'thesamwhichillettbemndinthe circulating liquid the p lyhydric alcohol and water are contin'um'mly flashed ofl, discharged from the evaporator and settles out 01' the 7 111i:

salt may be continuously or intermittently dis charged from the evaporator and washed with water to recover any of the liquid flash evaporation medium therefrom. The recovered liquid may be recovered from the salt solution and continuously or intermittently returned to the cycle.

The drawing illustrates diagrammatically an assembly of apparatus in which the process of the invention may be executed continuously. The assembly illustrated on the drawing is particularly well adapted to the recovery of a polyhydric alcohol such as a glycol, glycerol, etc., from its aqueous solution with a salt, said solution being contacted with a circulating oil heated to such a temperature that the polyhydric alcohol and water are flashed off, leaving the salt suspended in the oil.

Referring to the drawing, reference Figure 1 designates a supply tank or container for the polyhydric alcohol-water-salt solution to be treated. Tank I is provided with a suitable inlet for admission of the solution from any source, for example, a hydrolyzer (not shown). The solution is fed from tank I at the desired rate through valved conduit 2 into flash evaporator 5 wherein it comes into contact with a heated body of oil introduced into the flash evaporator continuously through conduit 6.

The flash evaporator 5 may be of any suitable material and type. The evaporator shown on the drawing is of special design adapted to use with a minimum of foaming and so designed asto permit continuous settling and removal of salt therefrom. The polyhydric alcohol-water-salt solution and the heated oil come into contact in the conical portion of element -3. The conical part of element 3 is open at the apex and partly submerged in the circulating oil. The conical portion of element 3 is preferably surrounded, as shown on the-drawing, by a suitable heating coil 4 through which any suitable heating medium such as steam, heated oil, etc., may be passed. The use of such auxiliary heating means may serve to reduce the amount of oil to be circulated through the oil circuit. By a proper regulation of the solution feed the foam formed on contact of the solution with the heated oil can be keptinside the portion of the cone which extends above the oil level in the evaporator. The lower part of the evaporator illustrated is cone shaped and provided at the lower portion thereof with a valved conduit provided with a valve or plug-cock throughwhich settled salt may be intermittently or continuously discharged from the evaporator. The oil containing suspended salt passes downward through the restricted part of the cone of element 3 into the lower portion of the evaporator where the salt .settles. out in the conical bottom thereof. The

clear oil passes upward on the outside of inner cone 3, and is discharged from evaporator 5 through conduit 1. Evaporator 5 may be provided with suitable sight-glasses (not shown) so that the oil level in the evaporator can be seen and kept substantially constant during the operation.

The oil leaves evaporator 5 through conduit I,-

passes into the suction side of circulating pump 8,

and is pumped through conduit 9 into oil heater The From heater I0, the heated oil is passed through conduit 6 into evaporator 5, completing the cir-' cult. The oil circuit may be equipped with a bypass line between conduits I and 9 near pump 8 to permit accurate regulation of the flow of oil through the circuit.

The flashed off vapors of the polyhydric alcohol and water leave evaporator 5 continuously through conduit II and pass into condenser I2 wherein they are condensed along with any oil vapors which might have been carried over with them. Condenser I2 may be of any suitable type. The condenser shown is of the jacketed tube type, cooling being effected by circulating a suitable cooling medium such as water through thejacket surrounding the tubes into which the vapors are passed. The condensate passes from the lower portion of condenser I2 into separator I 3. 0n the drawing, condenser I2 and separator I3 are shown as a unit of special design adapted to permit easy separation and return to the oil' circulating system any oil carried over with the polyhydric alcohol-water vapors. The oil, in case any is present, may be continuously or intermittently drained from the surface of the polyhydric alcohol-water solution in separator I3 and passed through valved conduit It into oil storage tank 26. Condenser I2 and separator I3 may, if desired, be separate units, and they may be of any suitable material and type. It is desirable that separator I3 be equipped with a suitable sightglass (not shown) so that the oil level therein may be easily seen and the rate of the discharge of the oil layer therefrom regulated. The polyhy-dric alcohol-water solution is conducted from the lower portion of separator I3 through conduit I5 into storage tank IS. The aqueous salt-free polyhydric alcohol solution may be conducted from tank' I6 through conduit I! to one or more recovery stages (not shown) wherein it is treated, for example, by distillation under reduced pressure. to separate water and obtain the polyhydric alcohol in an anhydrous or substantially anhydrous condition.

The salt which is'discharged from evaporator 5 through valve I8 into oil recovery tank I9 may carry considerable oil with it, the oil being adherent to the salt crystals. This oil is recovered and returned to the hot oil circuit by means of the oil recovery system which comprises oil recovery tank I9, settling tanks 22 and 23, and oil storage tank 26. The salt is dissolved in tank I9 by water introduced into the bottom portion of the tank through conduit 29'to provide mixing. Tank I9 may, if desired, be provided with additional stirring or agitating means to insure mixing and complete dissolving of the salt. I Water may be admitted to tank I9 continuously or intermittently. The salt solution and oil passes from the upper portion of tank I9 into cond'uit 2I from which it is discharged into settling or stratification tanks 22 and 23. In tanks 22 and 23, stratification occurs and the upper or oil layer is discharged therefrom into oil storage tank 26. The settling tanks may be operated in the following manner: Tank 22 is filled with the salt solution-oil mixture, and the mixture therein allowed to stratify. While the mixture in tank22 is stratifying, the liquid salt solution-oil mixture from tank I9 is run into tank 23. After stratification has occurred, sufiicient liquid is run into tank 22 from conduit 2I to float the oil layer through conduit 24 into oil storage tank 26. Settling tank; 23 may be used in like manner while the liquid from tank I9 is being run into settling tank 22. The oil layer is conducted from tank 23 into oil storage tank 26 through conduit 25. Tanks 22 and 23 are provided with outlet conduits 28 and 29, respectively, through which the salt solution, after separation of the oil therefrom, is discharged from the system. The oil from oil storage tank 26 may be returned to the oil circuit through valved conduit 21 which discharges into conduit 1.

Valves, pumps, temperature indicating means, pressure indicating means, heaters, coolers, etc., may be used in the illustrated system wherever deemed necessary or desirable.

The following table gives the data of two typical runs made-in accordance with the process of the invention employing an apparatus similar to that shown on the drawing. Ethylene glycol and water were flashed from a glycol-water-salt solution by contacting said solution with a heated oil.

In like manner, other polyhydric alcohols such as propylene glycol, the butylene glycols, the. amylene glycols, glycerol, alpha-methyl glycerol,

beta-methyl glycerol and the like as well as their homologues, analogues and suitable substitution products may be recovered from their aqueous solutions containing one or more salts. The process is also applicable with good results to the recovery of the polyhydric alcohol derivatives such as the oleflne oxides (ethylene oxide, propylene oxide, etc.) the glycidols (glycidol, alpha-methyl glycidol, beta-methyl glycldol, etc), the halohydrins (ethylene chlorhydrin, propylene chlorhydrin, glycerin monochlorhydrin, glycerin dichlorhydrin, etc.), and the like from their aqueous solutions containing one or more salts.

While I have described my invention in a detailed manner and illustrated suitable modes of executing the process thereof, it is to be understood that modiflcationsmay be made and that no limitations other than those imposed by the scope of the appended claims are intended.

I claim as my invention:

1. In a continuous flash distillation process for the recovery of ethylene glycol from an aqueous solution containing ethylene glycol and a dissolved salt, the steps which comprise continuously bringing the aqueous glycol-salt solution into contact with a circulating body of oil which is substantially immiscible with ethylene glycol and boils under the existing pressure at a temperature above that at which said flash distillation is effected and maintained at a temperature of from about 150C. to about 250 C. at such a rate that the ethylene glycol and water are continuously and substantially completely flashed off without substantial ethylene glycol decomposition, leaving the salt in the oil, withdrawing oil containing salt, separating salt from the withdrawn oil and heating and recycling the separated oil to the flash distillation stage.

, 2. In a flash distillation process for the recovcry of ethylene glycoFfr'om an aqueous solution containing ethylene glycol and a dissolved salt,

the steps which comprise contacting the aqueous glycol-salt solution with a body of a liquid boiling under the existing pressure at a temperature above that at which said flash distillation is effected and, which is substantially immiscible with ethylene glycol and water and in which salts are substantially insoluble, said liquid being maintained at a temperature sufllciently high to substantially completely flash off the ethylene glycol and water but below that at which substantial decomposition of said glycol takes. place, leaving the salt in the heated liquid, withdrawing salt containing. liquid,.separating salt therefrom and recycling the liquid to the flash distillation stage.

3. In a flash distillation process for the recovcry of a glycol from an aqueous solution containinga glycol and a dissolved salt, the steps which comprise contacting the glycol-water-salt solution with a body of oilwhich is substantially immiscible with and boils at a higher temperature than said glycol and in which said salt is substantially insoluble and maintained at a temperature sufiiciently high to substantially completely flash oil the glycol and water but below that at which substantial decomposition of said glycol takes place, leaving the salt in the oil, withdrawing oil containing salt, separating salt from the withdrawn oil and heating and recycling the separated oil to the flash distillation stage.

4. In a flash distillation process for the recovery of a glycol from an aqueous solution containing a glycol and a dissolved salt, the steps which comprise contacting the glycol-water-salt solution with a body of a liquid boiling under the existing pressure at a temperature above that at which said flash distillation is efiected and which is substantially immiscible with the glycol and the water, said liquid being maintained at a tem-' perature sufliciently high to substantially completely flash ofi the glycol and the water but below that at which substantial decomposition of said glycol takes place, leaving the salt in the heated liquid, removing salt from said liquid and contacting the liquid with more glycol-waterssalt solution.

5. In a flash distillation process for the recovv cry of a polyhydric alcohol from an aqueous solution containing a polyhydric alcohol and a dissolved salt, the steps which comprise contacting the polyhydric alcohol-water-salt solution with a liquid boiling under the existing pressure at a temperature above that at which said flash distillation is effected and which is substantially immiscible with the polyhydric alcohol and water and in which said salt is substantially insoluble, said liquid being maintained at a temperature suiiiciently high to substantially completely flash oil the polyhydric alcohol but below that at which substantial decomposition of said alcohol takes place, leaving the salt in admixture with the heated liquid, removing salt from said liquid and further contacting the liquid with polyhydric alcohol-water-salt solution.

6. In a flash distillation process for the recovery of an alcohol from an aqueous solution containing an alcohol and a dissolved salt, the steps which comprise contacting the aqueous alcoholsalt solution with a liquid boiling under the existing pressure at a temperature above that at which said flash distillation is effected and which is substantially immiscible with the alcohol and water and in which salts are substantially insoluble, said liquid being maintained at a temperature sufliciently high to substantially'comthan said alcohol and in which said salt is subpletely flash oi the alcohol and water but belowthat at which decomposition of said alcohol is substantial during said flash distillation, separating salt from said liquid and further contacting the liquid withsaid aqueous alcohol-salt solution.

7. A continuous process for the recovery of a polyhydricalcohol from an aqueous solution containing a polyhydric alcohol and a dissolved salt which comprises continuously feeding the aqueous alcohol-salt solution into a flash distillation stage wherein it is brought into contact with a circu-' lating body of oil which is substantially immiscible with and boils at a higher temperature stantially immiscible and maintained at a temperature sufiiciently high to substantially completely flash ofi the polyhydric'alcohcl and water and leave the salt in suspension in the oil but below that at which substantial decomposition of said alcohol takes place, continuously removing the'fiashed oif polyhydric alcohol and water vapors from the system withdraning oil containing said suspended salt, separating the salt from the oil, and heating and recycling the separated oil to the flash distillation stage.

JAN 1). RUYSQ 

